New azo dyes



Patented Jan. 6, 1931 J'OI-IANN HuIs ANN' nn HUGO soHwErrzER, F WIESDORF-ON-THE-B-PIINE,AND.

RICHARD scrfissnn, or oonoenn-nnu'rz, GERMANY, essienons TO G NE AL,

ANILINE WORKS, INC., OF NEW' YORKQNL Y., CORPORATION, OF DELAWARE new AZO DYES,

No Drawing. AppIica tion filed June 25, 1928, Serial No. 288,286, and in Germany July 451922. a

The present invention,concerns new and valuable azo dyestulls'of the general tormula: a

an 0antic-benzene-azo-aceto-acetic acid chloride dyestuff is caused to lnteractwvith an jarylannne sulionic acid or a nuclear substitution product thereof, preferably previously dissolved in a suitable solvent, such as for example, pyridine, or quiuoline, which at the same time serve for neutralizing the hydrochloric acid liberated during the re action. Thus are obtained monoazo dyestufis, sulfonatedin the acetoacetic arylide residue and therefore soluble in water. These dyestulis when precipitated as lakes and used as size colors yield deep and remarkably clear yellow to orange shades, which are fast to 1 light and water. Our new products are more over distinguished by the fact that they dye wool in very clear and even shades, remarkably fast to fulling and light.

Our new dyestuffs, after being dried and pulverized, are generally in the form of their alkali metal salts yellow to orange powders soluble in water and sulfuric acid with a yellow coloration, diflicultly soluble or insoluble in organic solvents. The color lakes prepared from them are distinguished by full yellow shades, clearness and iastness to light. The new products dye Wool evenly clear yellow shades of'superior fastness to light and fulling. v

The following examples will illustrate our invention, without limiting it thereto:

Ziaiample J.30l parts by weight of the J chloride produced from the dyest'ufl' e-chloro 2 mt1'o{benzene-1-azo-acetoacet1c acid: (F. P.-

are dissolved in about times the weightof chlorobenzene withgentle heating.

The solution' is cooled again to about 30 C. and a solution of 203- parts by weight 0f2? anisidinesulfonic: acid in about 151 times the Weight o-fpyridine is run: in with thorough stlrring also at 30 C.

when dissolved and precipitated in the customary. manner on substratum the dyestuff yields a clear yellow pigment lake, which whenused as a size color-exhibits an excellent fastness to water and light: The dye stu'fl'fis also ofinterest in weolidyeing,since it dyes woolvery evenly in yellow shades, last to fulhng and very fast to light.

Example 2. '207,5 parts by weight oi chloroanilineg-sulionic acid are dissolved at about 509 G, in times theweight of pyridine. A solution of 283.5 parts by eight of the dyestutl' 2-nitro-4l -toluene-1- azoacetic acid chloride (F. P. 157 C.) in 4200 parts by weight} of chlorobenzene is caused to run into this solution with thorough-stirring at a temperature of C. The condensation product begins to separate immediately, and can be separated "from the cooled reaction mixture by filteringf When was The; tempertureollithe reaction mixture rises'about 5 C.

The dyesufibeginsto separate soon and after "sometime can be separated from the liquor freed from adhering pyridine and chlorobenzene by means of steam in aqueous suspension, rendered alkaline with sodium car-r bonate, the dyestutf crystallizes in greenish yellow crystals. The dyestufi has in its free state the probable formula:

'Ihe pigmentlakeproduced from the same possesses a cleargreenish yellow shade and when used as size color possesses an excellent tastness to water-and Very satisfactory fastness to light. The dyestuff dyes 'woolvery;

even greenish'yellow shades ofsatisfactory fastness to light andfulling." 7 r To claim: i

1. In the process of preparing water-soluble mono-azo-dyestufis, the step whichcomprises j reacting with an. o-nitro-benzene-azo-aceto- 'aceticacid chloride dye'stuif upon a compound of the 'rou consistin of ar lamino sulfonic acids and nuclear substitution products thereof. 7 I V 2., In the process of prep aringwatersoluble mono-azo-dyestufi's, the step which comprises reacting with an o-nitro-benzene-azo-aceto-- acetic acid chloride dyestutl upon a compound of thegroup consisting of arylamino sulfonlc acids and nuclear substitution products thercof, dissolved in-an organic solvent of the group consisting of pyridine and quinoline.

3. In the process of preparing water-soluble mono azo-dyestufis, the step which comprises reacting with one molecule of 4-chloro-2- nitrobenzene-Lazo-acetoacetic acid chloride dyestufi upon one molecule of 2-anisidine-4- sulfonic acid. p L

4:. In the process of preparing water-soluble mono-azo-dyestufls, the step which comprises reacting with one] molecule of l-chloro-EZ:

position to the az o group and which may be further substitutedby any substituent with the exceptionof a sulfo group and R an 'aromatic nucleus which is substituted by a sul-fo group and which maybe further. substituted by any substituent,and being in the form of the alkali metal'salts yellow to orange powders, exhibiting various yellow shades of outstanding clearness and fastness to lightand water as size colors and dyeing wool clear yellow-shades of superior tastness to light and fullin 6. As a new product, the water soluble mono-aZo-dyestufi having in its free state most probably the following formula nitro-benzene-l-azo-aceto-acetic acid chloride dyestufi upon one molecule of 2-anisidine-4- ilfonic acid, dissolved 1n pyridme at a temperature of about 30 C. 1

5. As new products water soluble monoazo dyestuffs having most probably the formula om R-N:N (IJH wherein R represents an aromatic nucleus which is substituted bya nltro group in ortho- I ll) 

